Solid, thin chemiluminescent device

ABSTRACT

There is provided a flexible, thin, rectangular, chemiluminescent device comprised of a back sheet of a laminated metal foil having heat sealed thereto at its edges a bi-component front sheet, the first component of which is a laminated metal foil and the second component of which is a transparent or translucent polyolefin sheet, said first and second components being heat sealed to each other at their adjacent latitudinal edge, from about 20% to about 50% of the surface area of said front sheet being comprised of said first component; temporary separation means positioned so as to divide the interior area of said device into two compartments, one under each of said components, the compartment under said second component having positioned therein an absorbent material containing a solvent solution of an oxalate and, optionally, a fluorescer, and the compartment under said first component containing an activator solution.

BACKGROUND OF THE INVENTION

The production of devices capable of emitting light through chemicalmeans is well known in the art. Lightsticks, for example, are taught inU.S. Pat. No. 3,539,794 while other configurations have also been thesubject of many U.S. Pat. Nos. e.g. 3,749,620; 3,808,414; 3,893,938.Additional recent patents include U.S. Pat. No. 4,635,166 and U.S. Pat.No. 4,814,949.

The devices shown in FIG. 5 of U.S. Pat. No. 3,893,938 and FIGS. 5 and 8of U.S. Pat. No. 3,539,795 are those over which the devices of thepresent invention are an improvement. The devices of this type known inthe art fall for many reasons, not the least of which include theirinability to emit light over the required period of time, theirpropensity to emit poor quantities of light, their inability toconcentrate light in a centralized or uniform area and the like. Thedevices of the above two patents, for example, do not preventdegradation of the activator solution from loss of volatile componentsin that the activator solution is contained in a compartment having atransparent or translucent, permeable surface. Additionally, thematerial, when present, which is used to absorb the activator solutionupon activation of the device has not proven to be entirely successfulbecause of its failure to absorb the activator solution uniformly,thereby causing areas of no or dim light and areas of bright light inthe device.

SUMMARY OF THE INVENTION

The present invention relates to a flexible, thin, rectangular,chemiluminescent device comprised of a back sheet of a laminated metalfoil having heat sealed thereto, at its edges, a bi-component frontsheet, the first component of which is a laminated metal foil and thesecond component of which is a polyolefin sheet, said first and secondcomponents being heat sealed to each other at their adjacent latitudinaledge, from about 20% to about 50% of the surface area of said frontsheet being comprised of said first component; temporary separationmeans positioned so as to divide the interior area of said device intotwo compartments, one under each of said components, the compartmentunder said second component having positioned therein an absorbentmaterial containing a solvent solution of an oxalate and, optionally, afluorescer, and the compartment under said first component containing anactivator solution.

BRIEF DESCRIPTION OF THE DRAWING

The invention may better be understood by reference to the drawing inwhich:

FIG. 1 depicts a top view of the chemiluminescent device;

FIG. 2 depicts a side view of the chemiluminescent device showing theabsorbent material under the clear side of the top layer, a clamp as thetemporary separator and the activator solution in the secondcompartment.

FIG. 3 depicts an exploded side view of the chemiluminescent device.

DETAILED DESCRIPTION OF THE INVENTION INCLUDING PREFERRED EMBODIMENTS

The majority of commercial chemical lighting devices come in the shapeof plastic tubes. Whereas these devices are quite effective from thestandpoint of light emission, they are comparatively bulky and, as aconsequence of their round cross-section, they tend to emit light in alldirections rather than focus it in one direction. Thus, there has been aneed to produce chemical light devices which are thin, flat, flexible,stable, easy to handle and emit light in one direction.

Many of the above-described difficulties of chemiluminescent deviceshave been overcome by the instant invention whereby the activatorsolution is stored in a compartment which is totally comprised of ametal foil laminate. The metal foil enables the activator solution toretain its activity because it is impermeable.

Additionally, in a preferred embodiment, the absorbent material iscomposed of a unique polymer structure which enables the material to beused in a thin configuration and to result in a smooth, uniform surfacewhich does not absorb the light generated from the fluorescent reaction.

It is been found that an excellent device results when the absorbentmaterial is positioned in a compartment of the device having a lightemitting window with a reflective foil backing and the activatorsolution is contained in a compartment produced entirely of the samefoil as the backing.

The back sheet and the foil member of the bi-component front sheet ofthe instant invention are both a laminated metal foil, preferablyaluminum, which is comprised of, in superimposed relationship, 1)aluminum foil of from about 0.0001 to about 0.002 inch in thickness and2) low to medium density polyethylene or linear low to medium densitypolyethylene of from about 0.0005 to about 0.005 inch in thickness.

The low density polyethylene is adhered to the inside of the aluminumfoil with an acrylic acid copolymer adhesive.

The resultant aluminum foil laminate imparts to the device of theinstant invention: A) low or n permeability of volatile components ofthe activator solution, B) heat stability, C) no degradation, D) nodelamination between the back sheet and the bi-component front sheet. E)non-deteriorating heat sealability, F) stability of chemiluminescentcomponents and G) shelf life. Additionally, the laminate is receptive toself-adhering adhesives.

The total thickness of the aluminum foil laminate ranges from about0.001 to about 0.01 inch.

The acrylic acid copolymer adhesive is known and generally comprises acopolymer with ethylene. The adhesive contains up to about 10%, byweight, of acrylic acid. It is sold by Dow Chemical Company under thetradename Primacore®. The laminate foil can be prepared by extrusion ofa hot layer of the adhesive between the laminate layers, 1) or 2), orextrusion of the adhesive onto the foil followed by extrusion of thelayer 2) onto the adhesive coated foil or by mixing the acrylic acidcopolymer adhesive and the layer 3) in molten form and applying themixture to the foil unifomly over its surface.

The side of the foil opposite that having the polyethylene thereon maycontain a strength-imparting coating thereon such as orientedpolyethylene, nylon etc. or may be decorated, printed on etc.

The bi-component front sheet is produced from a first componentcomprising a polyolefin resin such as transparent or translucentpolyethylene, polypropylene etc. and a second component comprising thesame aluminum foil laminate as the back sheet. The two components of thefront sheet are heat sealed together at their adjacent latitudinaledges. The aluminum foil laminate comprises from about 20% to about 50%of the total surface area of the front sheet. The front sheet is fromabout 0.001 to about 0.01 inch in thickness.

Although it is preferred that the device be formed by heat scaling itsvarious components together, it is also possible to form the device bysonic welding and the like.

The device is separated into two compartments by the use of a temporaryseparation means such as rupturable seal, a clamp, a tight fold etc.,the main purpose of the separating means being to separate thechemiluminescent chemicals which, when combined, form chemical light.The preferred means is a clamp such as shown in the attached drawings,and as is known in the art.

The backside of the back sheet preferably has a self-adhering adhesivelayer applied thereto so as to enable the device to be adhered to anysubstrate or to itself in a wrap-around fashion.

As mentioned above, the compartment below the front sheet componentcomposed of the polyolefin has positioned therein an absorbent materialsuch as sponge, pad, mat, porous polymer etc. so as to absorb thechemiluminescent oxalate solution which comprises a solvent solution ofan oxalate and, optionally, a fluorescer, and also to absorb theactivator solution which is released from the second compartment uponactivation of the device. Although any such absorbent material may beused, a most preferred material is that disclosed and claimed incopending application, Ser. No. 07/612,844), filed concurrentlyherewith. The most preferred material is a porous, flexible.[.,plasticized.]. structure comprising A) a non-particulate phasecomprising a vinyl halide or vinylidene halide polymer having amolecular weight of about 100,000 to about 500,000 which constitutesabout 0.5 to about 15.0 weight percent of .[.the structure.]..Iadd.total polymer, .Iaddend.B) an agglomerated particle phasecomprising either 1) about 85.0 to about 99.5 weight percent .Iadd.oftotal polymer .Iaddend.of vinyl halide or vinylidene halide polymerparticles having a diameter of from about 25 to about 125 microns and amolecular weight of from about 50,000 to about 120,000, or mixtures ofsaid particles, or 2) about 45 to about 98.5 weight percent .Iadd.oftotal polymer .Iaddend.vinyl halide or vinylidene halide polymerparticles having a diameter of from about 25 to about 125 microns and amolecular weight of from about 50,000 to about 120,000, or mixtures ofsaid particles and about 1 to about 40 weight percent .Iadd.of totalpolymer .Iaddend.of of vinyl halide or vinylidene .Iadd.halide.Iaddend.polymer particles having a diameter of from about 130 to about225 microns and a molecular weight of from about 100,000 to about225,000 and C) a plasticizer comprising a solvent solution of achemiluminescent compound and, optionally, a fluorescer, dispersedthroughout both said phases.

The vinyl halide or vinylidene halide polymers useful in the productionof these structures are well known in the art. They include polyvinylhalides such as polyvinyl chloride and polyvinyl fluoride;polyvinylidene halides such as polyvinylidene chloride andpolyvinylidene fluoride; copolymers of vinyl halides and/or vinylidenehalides with hydrocarbons such as ethylene, propylene etc. in amounts ofup to about 25%, by weight, based on the total weight of polymerpreferably 5%-15%, by weight, same basis; copolymers of vinyl halidessuch as vinyl chloride/vinyl fluoride copolymers; copolymers ofvinylidene halides such as vinylidene chloride and vinylidene fluoride;copolymers of vinyl halides and vinylidene halides such as vinylchloride and vinylidene chloride; terpolymers of vinyl halides andvinylidene halides such as terpolymers of vinyl chloride, vinyl fluorideand vinylidene chloride; mixtures of the above vinyl halide polymers andvinylidene halide polymers; mixtures of vinyl halide or vinylidenehalide polymers and hydrocarbon polymers such polyvinyl chloride andpolyethylene m amount up to about 25%, by weight, based on the totalweight of polymers, of hydrocarbon polymer, preferably about 5%-15%, beweight, same basis.

Homopolymers and copolymers of vinyl chloride are preferred.

Useful plasticizer solvents are selected from dialkyl esters of phthalicacid, ethylene glycol ethers, citric acid esters or alkyl benzoates suchas ethyl benzoate, butyl benzoate etc. and are present in amounts offrom about 0.5 parts to about 3.0 parts of plasticizer per part of vinylhalide or vinylidene halide polymer. A preferred plasticizer solvent isdibutyl phthtalate and it is preferably used in a ratio of about 1.4part to about 1.0 part of polymer.

Useful chemiluminescent compounds are selected from3-aminophthalhydrazide, 2,4,5-triphenylimidazole,10,10'-dialkyl-9,9'-biacridinium salts9-chiorocarbonyl-10-methylacridinium chloride, andbis(substituted-phenyl) oxalate is bis(2-nitrophenyl) oxalate,bis(2,4-dinitrophenyl) oxalates. Useful oxalates include those suchbis(2,6-dichloro-4-nitrophenyl) oxalate, bis(2,4,6-trichlorophenyl)oxalate, bis(3-trifluoromethyl-4-nitrophenyl) oxalate,bis(2-methyl-4,6-dinitrophenyl) oxalate,bis(1,2-dimethyl-4,6-dinitrophenyl) oxalate, bis(2,4-dichlorophenyl)oxalate, bis(2,5-dinitrophenyl) oxalate, bis(2-formyl-4-nitrophenyl)oxalate, bis(pentachlorophenyl) oxalate, bis(1,2-dihydro-2oxo-1-pyridyl)glyoxal, bis-N-phthalmidyl oxalate,bis(2,4,5-trichloro-6-carbopentoxyphenyl) oxalate,bis(2,4,5-trichloro-6-carbobutoxyphenyi) oxalate orbis(2,4,6-trichlorophenyl) oxalate,bis(2,4,5-trichloro-6carbopentoxyphenyl) oxalate,bis(2,4,5-trichloro-6-carbobutoxyphenyl) oxalate andbis(2,4,6-trichlorophenyl) oxalate. The chemiluminescent compound isadded as a solution with the plasticizer solvent during the productionof the structure, and is present in an amount of about 10 weight percentto about 15 weight percent of the plasticizer solution. The preferredchemiluminescent compound is bis(2,4,5-trichloro-6-carbopentoxyphenyl)oxalate at about a 12% concentration in the plasticizer solvent,preferably dibutylphthalate.

Useful fluorescers are the substituted anthracenes such as9,10-bisphenylethynylanthracene, 1-chloro9,10-bisphenylethynylanthraceneor 2-chloro-9,10-bis(paramethoxyphenyl)anthracene and are used at aconcentration of about 0.1 weight percent to about 2.0 weight percent,preferably about 0.1 weight percent to about 0.3 weight percent, of theplasticizer solution, and is preferably added therewith during thepreparation of the structure.

The structures discussed above are prepared by a process which comprisesforming a uniform slurry of the resin particles in a plasticizer,forming the slurry into a shape and hating the shaped slurry to atemperature of from about 80° C. to about 150° C. for from about 5 toabout 50 minutes.

A preferred process of making the structures wherein a small portion,i.e. from about 0.5 to about 3.0 weight percent of vinyl halide orvinylidene halide polymer particles are first slurried alone in theplasticizer, optionally, containing the fluorescer, and the slurry isheated from about 80° C. to about 150° C. for about 5 minutes to about20 minutes to obtain a solution to which the remaining vinyl halide orvinylidene halide polymer particles are added and mixed to form theuniform slurry. The uniform slurry is then formed, preferably intosheets of about 0.1 mm to about 10 mm in thickness, preferably about1.0mm to about 3.0 mm in 10 thickness, and said sheets are then heatedto about 80° to about 150° C. for about 5 minutes to about 50 minutes,preferably at about 110° C.-130° C. for about 10-40 minutes or such thatexcess fusion does not occur.

The structure may be shaped, for example, by casting, molding, extrudingor blow molding the slurry, etc.

The desirable characteristics of the chemiluminescent polymer structuresare the following:

(1) Reasonable strength and flexibility.

(2) Good absorptivity so the chemiluminescent reaction can be initiatedby contacting the PVC structure with an activator solution. halides suchas vinyl chloride/vinyl fluoride copolymers;

(3) Uniform surface appearance.

(4) The structure must not interfere with the chemiluminescent reaction.

(5) Good shelf-life.

(6) The chemiluminescent structure should be translucent.

These properties of the polymer structure are determined in large partby the following factors:

(1) The amount of chemiluminescent solution absorbed into the polymerstructure.

(2) The particles size distribution and molecular weight distribution ofthe polymer particles used.

(3) The rate of heating and the heating time employed during curing.

(4) The amount of polymer that becomes dissolved into thechemiluminescent solution.

The structures contain one or more components of the chemiluminescentreaction. The components of the chemiluminescent reaction areincorporated into the structure by any number of means but the preferredmethod is to dissolve the components of the chemiluminescent reaction ina solvent that swells the vinyl halide or vinylidene halide polymer, andthe preferred solvent for this process is dibutylphthalate. The amountof chemiluminescent solution used to swell the polymer varies betweenabout 5 and 90 weight percent; the preferred amount is between about 25and 80 weight percent, most preferably, about 55-60 weight percent. Anychemiluminescent reaction that is compatible with the matrix material ofthe sheet may be used; the preferred chemiluminescent reaction being theperoxy-oxalate reaction with the preferred oxalate ester being acarbopentoxyphenyloxalate. Preferred fluorescers for thischemiluminescent reaction are substituted anthracenes. The structure iscapable of absorbing an activator in order to start the chemiluminescentreaction. It is necessary for the structure to absorb at least oneequivalent of the activator solution, but it is preferred that thestructure absorb three equivalents of the activator solution.Alternatively, the components of the chemiluminescent reaction can beincorporated into the structure after the structure is formed byabsorbing the components into the pores of the structure by merelysoaking the structure in a solution of the component.

In order to prepare an absorptive, porous, flexible, strong vinyl halideor vinylidene halide polymer structure with good surface appearance, ithas been found that a mixture of two, or preferably three, vinyl halideor vinylidene halide polymer powders selected from fine, medium andlarge particle size powders, where at least one of the powders is a fineparticle powder, is required. Major deviations from the above describedprocess yields structures that are not capable of effectively absorbingactivator solution or are physically not acceptable i.e. they are flakyor too fused to be useful.

With reference to the drawing, specifically FIG. 3, the exploded view,the laminated aluminum foil back sheet 1 is heat sealed at points 2,3and 4 to the front sheet which comprises a bi-component configuration ofsheet 5 and another sheet 6 of the laminated aluminum foil. An absorbentmaterial 7 is positioned between sheets 1 and 5, which, whenconsolidated form compartment 8, whereas compartment 9 is formed whenthe device is formed by consolidating sheets 1 and 6. Compartment 9 isshown containing activator solution. Adhesive layers 10 are positionedon the reverse side of layer 1 and are protected from damage orpremature adhesion by peel-off covering sheets. Clamp 11 is shown as thecompartment separating means and is comprised of a receptive member 12and a pin 13 which 25 is held into member 12 by friction as best seen inFIG. 2. FIG. 1 shows the areas of heat sealing by cross-hatching.

The following examples are set forth for purposes of illustration onlyand are not to be construed as limitations on the present inventionexcept as set forth in the appended claims. All parts and percentagesare by weight unless otherwise specified.

The following abbreviations are sometimes used to indicate chemicalstructures, analytical tests and other repeatedly used items.

PVC: Polyvinyl Chloride

Fine Particle PVC: A dusty, white powder of medium viscosity PVC resinhaving a molecular weight of about 303,000 and an average particle sizeof 0.20-1.5 microns.

Medium Particle PVC: A white powder of PVC resin produced by masspolymerization having a molecular weight of about 98,000 and an averageparticle size of 70-75 microns.

Large Particle PVC: A white powder of PVC resin having a molecularweight of about 205,000 and an average particle size of 150 microns.

CPPO: Bis(2,4,5-trichloro-6-carbopentoxyphenyl) oxalate, the oxalateester used in the chemical light reaction.

BPEA: The fluorescer used in the green chemical light reaction is9,10-bis(phenylethynylanthracene).

CBPEA: The fluorescer used in the yellow oxalate solution is1-chloro-9,10-bis(phenylethynylanthracene).

BPEN: The fluorescer used in the blue oxalate solution is2-chloro-9,10-bis(p-methoxyphenyl) anthracene.

Activator: A dimethylphthalate solution of hydrogen peroxide and sodiumsalicylate.

Spotmeter: Instrument used to measure the light output intensity of achemical light reaction over time. This instrument is made by KollmorgenCorporation, Model UBDl/4.

TLOP: Total light output.

Glow Time: The time required to emit 90% of the total light generated bythe structure.

LDPE: Low density polyethylene.

OPP: Oriented polypropylene.

EAA: Ethylene/acrylic acid copolymer (90/10)

LLDPE: Linear, low density polyethylene

TOTAL LIGHT OUTPUT MEASUREMENTS

The following method is the standard test used herein for measuringtotal light outputs of samples. The sample is prepared and cut into1"×21/2" pieces. These test pieces are placed inside 13/8"×33/4", 1.5mil thick, polypropylene bags. The openings of these bags are then heatsealed just above the contained sample, leaving a tab of polypropyleneat what was the open end of the polypropylene bag for hanging it infront of the spotmeter. The test pieces are activated by injecting theactivator solution into the polypropylene bags with a syringe. The mountof activator used depends on the thickness of the sample. Usually 1.5ml. of activator is required for a 3-4mm thick sample. The bags are hungvertically during testing and the syringe needle is inserted into thebag near the top.

The spotmeter is focused on the center of the bag at a distance of threeinches to one foot. Up to eight samples can be tested simultaneously byplacing them on an eight position carousel holder. The carousel andspotmeter are under computer control allowing for both data acquisitionand control of the sample positioned in front of the spotmeter.

The samples are activated 10 sec. apart and the data acquisition started2 min. after the first sample is activated. The computer is set tochange samples every 10 sec. The run duration and maximum spotmeterscale depend on the concentration of catalyst in the activator solution.The usual settings for activator containing 0.0043, weight percent,sodium salicylate catalyst are 6 hr. duration and 0-199 ft. lm (aspotmeter setting of 10¹ for green and yellow test samples, and aspotmeter setting of 100 for blue test samples).

The surface appearance while glowing, as well as, the total lightoutput, the glow time, the mechanical strength, and the absorptivitymust be considered in the optimization of a chemiluminescent product.Variations in catalyst concentration in the activator solution cause theglow time of activated structures to vary between 30 min. and 6 hr. Thebest light outputs are obtained at glow times of about 4 hr. Activationof the structures requires about 0.2-0.25 part of activator solution perpan of structure. The brightness of the structure depends on itsthickness. Without a reflective support, the brightness increases withincreasing thickness. The brightness of a thick structure can beduplicated with a thinner structure that has a reflective backing. Agood working thickness is about 3-4mm with a reflective backing facingthe front of the structure.

EXAMPLE OXALATE SOLUTION PREPARATION

Dibutylphthalate (864 parts) is added to a suitable dry vessel that hasbeen purged with nitrogen and fired with an overhead stirrer,thermocouple thermometer, nitrogen inlet adapter and heating mantle.This solvent charge is heated to 50° C. Fluorescer is added and themixture is stirred for 30 min. while the temperature is maintained at50° C. CPPO (133 parts) is added and the solution is stirred at 50° C.for an additional 2 hours. The mixture is allowed to cool to roomtemperature and filtered under a nitrogen atmosphere through a mediumfrit sintered glass funnel.

The oxalate formuations for application in the structures are shown inthe table below.

    ______________________________________                                        Color        Formulations                                                     ______________________________________                                        Blue         12 wt % CPPO 0.2 wt % BPEN                                       Green        12 wt % CPPO 0.15 wt % BPEA                                      Yellow       12 wt % CPPO 0.25 wt % CBPEA                                     ______________________________________                                    

The amounts of the fluorescers and CPPO are adjusted to take intoaccount the relative purities of the materials so that the activecomponents of the oxalate solution will be present in the amounts shownin the table above.

EXAMPLE 1 LAMINATED ALUMINUM FOILS

The following foils are prepared and tested. The layers of the laminatesare listed wherein, when formed into a device in accordance with thisinvention, the first listed material becomes the outer layer of thedevice and the last listed layer is on the inside of the device. Testresults are listed with each foil laminate.

    ______________________________________                                        Structure                                                                     ______________________________________                                        Laminate 1 75 gauge OPP (oriented polypropylene)                                         (0.00075") optional strength                                                  imparting                                                                     1.5 lb/3000 sq. ft. Lamal white adhesive                                      (0.0001")                                                                     Al foil (0.00035")                                                            10 lb/3000 sq. ft. EAA (Primacor ® 3440)                                  (0.00067")                                                                    LDPE (0.001")                                                                 TOTAL THICKNESS = 0.0029"                                          ______________________________________                                    

Optimized Sealing Conditions

Before exposure to activator, the heat seal peel force is 7 lbs. perlinear inch when sealed with 1.0 sec. impulse heating, 2.5 sec. cooling,and 30 psig pressure on seal area during sealing. After exposure toactivator overnight at room temperature, the heat seal peel force is 4lbs. per linear inch when sealed with 0.5 sec. impulse heating, 2.0 sec.cooling, and 30 psig pressure on seal area during sealing. These areoptimized sealing conditions.

Delamination Testing

Sealing conditions are 0.8 sec. impulse heating, 2 sec cooling, and 20psig pressure on seal area during sealing. After 31 days at 140° F. andat 150° F. no signs of blistering or delamination are noted.

Sealing Strength

Sealing conditions are 0.8 sec. Impulse heating, 2 sec. cooling, and 20psig pressure on seal area during sealing Seal peel strength beforeexposure to activator is 7.3 lbs. per linear inch. Seal peel strengthafter exposure to activator overnight at room temperature is 4.0 lbs.per linear inch.

Burst Test on 2"×3" Bags

Sealing conditions used are 0.8 sec. impulse heating, 2 sec. cooling,and 20 psig pressure on seal area during sealing. Bags burst at 18.6psig, no exposure to activator. Foil laminate fails; heat seal does notfail. Bags burst at 18.3 psig, after exposure to activator overnight atroom temperature. Heat seal does not fail; foil laminate fails inside ofheat seal. Bags burst at 15 psig after 31 days exposure to activator at140° F. and at 150° F.

Results

This laminate passes all stringent tests.

    ______________________________________                                        STRUCTURE                                                                     ______________________________________                                        Laminate 2 48 gauge PE (polyester) (0.00048") for                                        strength                                                                      1.5 lb/3000 sq. ft. adhesive                                                  (0.0001")                                                                     Al foil (0.00035")                                                            10 lb/3000 sq. ft. EAA (Primacor ® 3440)                                  (0.0067")                                                                     LLDPE (linear low density polyethylene)                                       (0.0025")                                                                     TOTAL THICKNESS = 0.0041"                                          ______________________________________                                    

Optimum Sealing Conditions

1.0 sec. inpulse heating, 1.5 sec. cooling, and 20 psig pressure on sealarea during sealing.

Delamination Testing

Optimum conditions are used. Delimination is noted on these samplesafter 4 days at 140° F. and 150° F. Delamination occurs by separation ofthe polyethylene heat seal layer from the Primacor® layer.

Sealing Strength

Optimum sealing conditions are used. Seal peel strength before exposureto activator is 19.2 lbs. per linear inch. Seal peel strength afterexposure to activator overnight at room temperature is 14.8 lbs. perlinear inch.

Burst Test on 2"×3" Bags

Optimun sealing conditions are used. Bags burst at 41.2 psig beforeexposure to activator. Bags burst at 34 psig (140° F.) and at 43 psig(150° F.) after exposure to activator for 6 days at their testtemperatures.

Results

This laminate is deficient in that it delaminates after 4 days inactivator solution.

    ______________________________________                                        STRUCTURE                                                                     ______________________________________                                        Laminate 3   60 gauge Nylon (0.0006") for strength                                         LDPE (0.00125")                                                               Al foil (0.00035")                                                            LDPE (0.00325")                                                               TOTAL THICKNESS = 0.00055"                                       ______________________________________                                    

Delamination Testing

Some signals of delamination after one day at 110° F. Completedelamination after 14 days at 110° F. Complete delamination after onedate at 150° F.

Burst Test on 2"×3" Bags

Bags are sealed for this test as follows: 1 25 sec. impulse heating, 5sec. cooling and 40 psig pressure on seal area during sealing. Bagsburst at an average value of 46.4 psig prior to exposure to activatorsolution. Bags burst at an average of 13.2 psig after exposure toactivator solution overnight at room temperature.

Results

This laminate fails by delamination.

    ______________________________________                                        STRUCTURE                                                                     ______________________________________                                        Laminate 4 48 gauge polyester (0.0048") for strength                                     Al foil (0.00035")                                                            4 lb/3000 sq. ft. Primacor ® 3440                                         (0.00027")                                                                    18 lb/3000 sq. ft. LDPE (0.0012")                                             TOTAL THICKNESS = 0.0023"                                                     NOTE: The Primacor ® and the LDPE                                         are coextruded.                                                    ______________________________________                                    

Delamination Testing

Sealing conditions are 1.25 sec. impulse heating, 5.0 sec. cool, 44 psigpressure on the seal area during sealing. Blisters after 25 days at 150°F. No delamination after 61 days at 150° F.

Sealing Strength

1.4 sec. impulse heating, 5.0 sec. cool, 40 psig pressure on the sealduring sealing. Peel strength=5.5 lbs. per linear inch (no exposure toactivator)

Laminate Peel

1.1 lbs. per liner inch (no exposure to activator)

50,000 ft. Exposure

Fails at 47 and 54 days; passes at 61 days.

Results

This laminate is unacceptable. The seal fails after exposure toactivator solution.

    ______________________________________                                        STRUCTURE                                                                     ______________________________________                                        Laminate 5:                                                                              100 gauge biaxially oriented Nylon                                            (0.001") for strength                                                         7 lb/3000 sq. ft LDPE adhesive (0.00047")                                     Al foil (0.00035")                                                            4 lb/3000 sq. ft. Primacor ® 3440                                         (0.00027")                                                                    18 lb/3000 sq. ft. LDPE (0.00012")                                            TOTAL THICKNESS = (0.00033")                                                  NOTE: The Primacor ® and LDPE                                             are coextruded.                                                    ______________________________________                                    

Optimized Sealing Conditions

1.5 sec. impulse heating, 4.0 sec. cooling, 30 psig pressure no sealarea during sealing.

Delamination Testing

Sealing conditions are 1.25 sec. impulse heating, 5.0 sec. cooling, 40psig pressure on seal area during sealing. Blistering does not occurafter 60 days at 150° F. No delamination after 64 days at 150° F.

Sealing Strength

Uses optimized sealing conditions. Seal peel strength before exposure toactivator is 7.1 lbs. per linear inch. Seal peel strength after exposureto activator at room temperature overnight 0.8 lbs. per linear inch.

Laminate Peel

0.75 lbs. per linear inch (no exposure to activator).

50,000 Ft. Exposure

Shows variable results in that it fails at 51 days, but passes at 35,59, and 64 days.

Burst Test on 2"×3" Bags

Uses optimized sealing conditions. Bags burst at 22.7 psig. no exposureto activator. Laminate fails at inside edge of seal. Bags burst fromfailure in seal at 5.0 psig after exposure to activator at roomtemperature overnight.

Results

This laminate also fails by heat seal degradation upon contact withactivator solution.

EXAMPLE 2

A chemiluminescent device is assembled in the following manner: A 47/8inch×2 inch transparent polyethylene sheet is heat sealed on one end(with a 1/8 inch overlap for the heat seal) to a 37/8 inch×2 inchsection of Laminate 1 sheet, as described in Example 1. The resultant81/2 inch×2 inch sheet is then sealed at the top and bottom lengthwiseedges to a 81/2 inch×2 inch sheet of Laminate 1 whereby an elongatedopen tube is formed with 1/8 inch heat seals on each edge and wherein inthe low density polyethylene (LDPE) layer of the foil laminate is on theinside of the tube, both for the back and front sheets of the tube. Onthe back of the tube is placed an adhesive backing covered with releasepaper.

Into the end of the tube containing the clear polyethylene front sheetis placed an absorbant material that is 1 5/16"×41/2"×3 mm in sizecontaining oxalate and yellow fluorescer. The end of the tube is sealedwith a 1/8 inch heat seal. The absorbent material is retained in placeby placing a compression seal clip and pin across the portion of thetube in which both the front and back sheets are foil laminate at adistance of 31/8 inch in from the remaining open end. Into the remainingportion of the tube is placed 3.5 ml. of activator solution. The end ofthe tube is closed with a 1 inch heat seal. In so doing, the activatorsolution is enclosed in a pouch that is composed completely of foillaminate. The compression seal clip and pin completely prevent mixing ofthe activator with the absorbant material until such time as thecompression seal is released.

Activation of the resultant device creates a total light output of 61.6ft.-lam.-hrs. The light piece has the advantage of being a flat,flexible, stable light source that can be attached to most solidsurfaces and is useful as a chemical light source. No degradation of theactivator solution of a similar non-activated device occurs after monthsof unprotected storage.

EXAMPLE 3

Fine particle size PVC is sifted through a fine wire screen to removelarge particles. The fine particle size PVC (10 parts) is thenthoroughly mixed with a small mount of the oxalate solution of Example Ato form a thick paste. The thick paste is slowly added to the remainderof 268 parts of the oxalate solution with vigorous agitation. A nitrogenatmosphere is maintained over the slurry so as to protect it fromatmospheric moisture and the slurry is heated rapidly to 100° C.-110° C.in about 5-10 minutes and maintained at this temperature for 10-15minutes. The PVC dissolves and the resultant solution becomes moreviscous. The solution is cooled to 50° C.-60° C. and 270 parts ofoxalate are added with stirring. 288 Parts of medium particle size PVCand 86.1 parts of large particle size PVC are added through a powderfunnel. The slurry becomes very thick and is stirred manually with aspatula into a smooth mixture.

90 Parts of the mixture are poured into a 5×8 inch glass-bottomed form,heated in an oven at 110° C.-120° C. for 10 minutes, removed from theoven and allowed to cool to room temperature. The cooled structure iseasily pealed from the form and cut into samples for testing. Thestructure is about 4mm thick. Addition of the activator solution ofExample B, below, results in the production of chemiluminescent light.

EXAMPLE B ACTIVATOR SOLUTION

An activator solution is prepared by stirring together 81.4 parts ofdimethyl phthalate, 13.3 parts of t-butyl alcohol, 5.29 parts of 90%aqueous hydrogen. peroxide and 0.043 part of sodium salicylate untilcomplete solution occurs.

EXAMPLE 4

Structures are prepared by slurrying together 14 parts of oxalatesolution and varying amounts of fluorescer with 10 parts of a PVCparticle mixture of 2.0 parts of large particle PVC, 7.5 parts of mediumparticle PVC and 0.5 part of fine particle PVC. Each slurry is baked inan oven at 120° C. for 10 minutes, and the result structure is cooled toroom temperature and cut into 1×3 inch strips which are then sealed inpolypropylene bags. The structures are activated by injecting 1.6 partsof activator solution of Example B into the bag and mixing. Theactivated structures in the bags are placed in front a spotmeter at adistance of 3 inches. Data is collected beginning two minutes afteractivation. The results are set forth in Table I, below.

                  TABLE I                                                         ______________________________________                                        COLOR    FLUORESCER (WT %)                                                                              TLOP (FT-L-HR)                                      ______________________________________                                        YELLOW   0.25             71.1                                                YELLOW   0.30             67.9                                                YELLOW   0.35             73.5                                                GREEN    0.15             47.9                                                GREEN    0.20             46.3                                                BLUE     0.07              7.09                                               BLUE     0.11              8.87                                               BLUE     0.14              9.40                                               BLUE     0.20              10.06                                              BLUE     0.25              13.51                                              ______________________________________                                    

EXAMPLE 5 TLOP VS CPPO CONCENTRATION

Structures are prepared as described in Example 4. The oxalate solutionsused in this example contain varying amounts of CPPO. The fluorescerconcentrations are 0.1 weight percent BPEN for the blue oxalate, 0.11weight percent BPEA for the green oxalate, and 0.26 weight percent CBPEAfor the yellow oxalate. The structures are activated and the TLOPmeasured, as described above. The results are shown in Table II, below.

                  TABLE II                                                        ______________________________________                                        COLOR      CPPO (WT %) TLOP (FT-L-HR)                                         ______________________________________                                        YELLOW      8          39.6                                                   YELLOW     11          46.2                                                   YELLOW      15*        71.1                                                   YELLOW     17          66.8                                                   GREEN       4           8.98                                                  GREEN        7.8       15.2                                                   GREEN      12          27.4                                                   GREEN       15*        26.2                                                   BLUE         3.7        2.35                                                  BLUE         7.7        6.47                                                  BLUE         11.7       8.87                                                  BLUE         14.2*      7.80                                                  ______________________________________                                         *The CPPO slowly precipitates out of this oxalate solution.              

EXAMPLE 6 TLOP VS OXALATE:PVC RATIO

Structures are prepared by slurrying together vary ing mounts of yellowfluorescer oxalate solution with PVC powder (10 parts) directly in asuitable vessel. The PVC powder mixture is composed of large particlesize 20 PVC (2.0 parts), medium particle size (7.5 parts) and fineparticle size PVC (0.5 part). These slurries are baked in an oven at120° C. for 10 min. The baked PVC is cooled and cut into 1×3 inch stripswhich then are sealed in polypropylene bags. The strips are activated byinjecting 1.6 parts of activator into the polypropylene bag. The bagsare placed in front of the spotmeter at a distance of 3 inches. Datacollection from the spotmeter is begun 2 min. after activation. Theresults of this study are shown in Table III, below.

The light output increases and then levels off at a ratio of about1.4:1. The structure is strong and does not crumble during or after thebaking stage of the preparation. When lower oxalate/PVC ratios areemployed, the resultant structures are flaky and cannot be handled.Higher oxalate/PVC ratios result in structures that are over plasticizedand not very absorptive of the activator solution.

                  TABLE III                                                       ______________________________________                                        ACTIVATOR    OXALATE/PVC   TLOP                                               (PARTS)      RATIO (WT:WT) (FT-L-HR)                                          ______________________________________                                         9           0.9:1         28.2                                               10           1.0:0         29.2                                               11           1.1:1         31.1                                               12           1.2:1         30.8                                               13           1.3:1         34.8                                               14           1.4:1         40.7                                               15           1.5:1         38.6                                               17           1.7:1         38.9                                               ______________________________________                                    

EXAMPLE 7 TLOP VS STL THICKNESS

Structures are prepared from yellow fluorescer oxalate solutions asdescribed in Example 3. The thickness of the structures is controlled byusing molds of different area and varying the mount of slurry used. Themolds, weights of slurry used, and the resulting thickness of thestructures after baking are shown in Table IV.

                  TABLE IV                                                        ______________________________________                                        SLURRY WEIGHT                                                                 (PARTS)       MOLD       THICKNESS (MM)                                       ______________________________________                                        10            90 mm dish 1.3                                                  45            5 × 8 inch                                                                         1.9                                                  15            90 mm dish 2.3                                                    67.5        5 × 8 inch                                                                         2.9                                                  20            90 mm dish 3.4                                                  90            5 × 9 inch                                                                         3.7                                                  25            90 mm dish 4.2                                                  35            90 mm dish 5.1                                                  40            90 mm dish 7.0                                                  ______________________________________                                    

The structures are cut into 1×21/2 inch pieces, activated with theactivator solution of Example B, and their TLOP measured. The mount ofactivator used in proportion to the thickness of the structure. Theresults are shown in Table V.

                  TABLE V                                                         ______________________________________                                        STL PAD      BRIGHTNESS                                                       THICKNESS (MM)                                                                             (FT-L)       TLOP (FT-L-HR)                                      ______________________________________                                        1.9          57.5         36.0                                                2.9          68.1         41.4                                                3.4          59.0         44.4                                                3.7          --           56.0                                                4.2          62.6         51.9                                                5.1          69.6         66.6                                                7.0          93.3         78.8                                                ______________________________________                                    

The TLOP of the structures is also measured for those of the samethickness; with and without reflective aluminum foil backing. Theresults are shown in Table VI.

                  TABLE VI                                                        ______________________________________                                                  WITH OR                                                             THICKNESS WITHOUT      BRIGHTNESS  TLOP                                       (MM)      FOIL BACKING (FT-L)      (FT-L-HR)                                  ______________________________________                                        1.9       with         70.2        46.1                                       1.9       without      57.5        36.0                                       2.9       with         96.7        61.6                                       2.9       without      68.1        41.4                                       3.4       with         62.1        57.1                                       3.4       without      59.0        44.4                                       3.7       with         --          63.7                                       3.7       without      --          56.0                                       ______________________________________                                    

EXAMPLE 8 CATALYST CONCENTRATION STUDIES

A series of tests is performed on the yellow, green, and blue structuresto determine the effect of catalyst concentration in the activator onthe TLOP and glow time. The glow time is taken to be the time periodfrom activation until 90% of the possible light output has been givenoff. The structures are prepared in the same way as those described inExample 3. The 1×2 inch samples are sealed in polypropylene bats andactivated by injecting 1.5 ml of the activator into the bag. Thecatalyst (sodium salicylate-NaSal) concentration in the activator isvaried. The light output is measured with the spotmeter at a distance ofone foot from the samples. Table VII sets forth the results.

                  TABLE VII                                                       ______________________________________                                                    YELLOW STL                                                        Parts NaSal TLOP (FT-L-HR)                                                                              GLOW TIME                                           ______________________________________                                        0.009       57.3          436                                                 0.019       64.6          267                                                 0.029       63.1          158                                                 0.043       57.3          95                                                  0.050       57.3          85                                                  0.062       48.1          65                                                  0.071       41.4          57                                                  0.082       40.1          44                                                  0.087       39.6          39                                                  ______________________________________                                                    GREEN STL                                                         Parts NaSal TLOP (FT-L-HR)                                                                              GLOW TIME                                           ______________________________________                                        0.009       43.0          330                                                 0.019       47.4          217                                                 0.029       43.3          119                                                 0.043       42.3          80                                                  0.050       41.6          90                                                  0.062       39.4          74                                                  0.071       38.9          62                                                  0.082       35.5          44                                                  0.087       34.4          42                                                  ______________________________________                                                    BLUE STL                                                          Parts NaSal TLOP (FT-L-HR)                                                                              GLOW TIME                                           ______________________________________                                        0.009        8.6          412                                                 0.019       10.0          324                                                 0.029        9.4          209                                                 0.043        9.3          111                                                 0.050        9.1          108                                                 0.062        8.2          79                                                  0.071        9.5          52                                                  0.082        8.6          38                                                  0.087        7.6          36                                                  ______________________________________                                    

EXAMPLE 9 ACTIVATOR ABSORPTION STUDIES

Three different oxalate-PVC mixtures are prepared that vary in the mountof fine particle PVC used in the PVC pan of the formulation. Yellowfluorescer-oxalate solution is used in a ratio of 1.4:1 (wt/wt) with thePVC mixtures shown in the following table. 35 PVC Particle Size

    ______________________________________                                        PVC Particle Size                                                             FORMULATION  FINE      MEDIUM     LARGE                                       ______________________________________                                        No. 1        2.6 wt %  75 wt %    22.4 wt %                                   No. 2        3.8 wt %  75 wt %    21.2 wt %                                   No. 3        5.7 wt %  75 wt %    19.3 wt %                                   ______________________________________                                    

The fine particle PVC is dissolved in the oxalate 45 solution at 100° C.The resultant solution is cooled to room temperature and the remainingmedium and large PVC is added. Portions of 24 parts of these slumes arepoured into molds and baked in an oven at 120°0 C. for 10 min. Theresulting structures are cooled and cut into 1 inch squares. The dryweights of these squares are recorded. These samples are placed in avessel containing activator solution at room temperature. The weightgain of these samples is taken at 1,2,3,5, and 10 min. intervals. Theresults are shown on Table VIII titled Activator Absorption where pansof activator absorbed per part of sample is measured against time. Thestandard commercial chemical lightstick contains 2.8 parts of activatorand 7.8 parts of oxalate solution. On a weight of active chemical basis,this corresponds to the absorption of 0.21 part of activator per part ofsample. It can be seen from Table VIII that the samples obtained fromPVC formulation No. 1 absorb the required mount of activator in about 2min. The other formulations, No. 2 and No. 3, do not absorb the neededamount of activator.

                  TABLE VIII                                                      ______________________________________                                        ACTIVATOR ABSORPTION                                                          No. 1         No. 2         No. 3                                             2.6% Fine PVC 3.8% Fine PVC 5.7% Fine PVC                                     Time    Wt.       Time    Wt.     Time  Wt.                                   Min.    Gain      Min.    Gain    Min.  Gain                                  ______________________________________                                        1       0.13      1        0.007  1     0.025                                 2       0.21      2       0.09    2     0.025                                 3       0.24      3       0.10    3     0.027                                 5       0.25      5       0.11    5     0.030                                 ______________________________________                                    

EXAMPLE 10 ENVIRONMENTAL MOISTURE EXPOSURE STUDIES

Structures are made by mixing large (13.75 parts), medium (29.7 parts),and fine (2.75 parts) particle PVC, and yellow fluorescer oxalatesolution (63.8 parts) in a blender. The resulting slurry is poured intoa rectangular-form and baked in an oven at 120° C. for 10 min. Thestructure is allowed to cool and cut into 1×3 inch strips. Approximately50 of these test strips are made by repetition of this procedure. Thesesamples are suspended from a "line" in the dark. Also in the dark areapproximately 50 open vials containing samples of the same yellowfluorescer oxalate solution used in the preparation of the structures.The temperature and humidity are monitored. The relative humidityaverages around 55% and the temperature varies between 20° C.-25° C. TheTLOP of the structures and lightsticks made from the oxalate stored inthe open vials, are taken about once a week. These light outputexperiments are conducted by taking a random sample of three of thestructures and sealing them in polyethylene bags. These bagged samplesare placed three inches in front of the spotmeter and activated byinjecting 1.6 ml. of high activator into the bag. Three lightsticks arealso prepared from the oxalate solution that was stored in the openvials. These lightsticks are prepared with ampoules of the sameactivator solution that is used to activate the bagged samples. Theamount of oxalate and activator used in these lightsticks is 7.8 partsand 2.8 parts, respectively. The lightsticks are also placed threeinches in front of the spotmeter and data collection is started twominutes after activation. The average TLOP of the three bagged samplesand the three light sticks at different exposure times are shown inTable IX, below.

                  TABLE IX                                                        ______________________________________                                        EXPOSURE  TLOP LIGHTSTICK                                                                              TLOP STRUCTURE                                       (WEEKS)   (FT-L-HR)      (FT-L-HR)                                            ______________________________________                                        0         111.3          43.2                                                 1         100.1          44.3                                                 2         92.7           41.7                                                 3         71.6           40.1                                                 4         77.4           41.3                                                 5         70.1           37.4                                                 6         69.2           38.2                                                 8         54.9           34.9                                                 10        14.4           --                                                   12         9.7           18.7                                                 ______________________________________                                    

It is apparent that the light output of the PVC structure samples decaysmore slowly than the light output of the exposed oxalate solution. It isnecessary, however, to protect the structures with a moisture barrierduring storage in order to maintain their shelf life.

EXAMPLE 11 FLUORESCENT LIGHT EXPOSURE STUDIES

Yellow light emitting structures are prepared from oxalate containing 12parts of CPPO end 0.25 part of CBPEA. Green light emitting structuresare prepared from oxylate containing 12 parts of CPPO and 0.15 part ofBPEA and blue light emitting structures are prepared from oxalatecontaining 12 part of CPPO and 0.2 part of BPEN. The structures used inthese tests are cut into 1×2 inch strips and sealed in polypropylenebags. The bagged samples are placed under a fluorescent light fixturefitted with two F40/)CW, cool white, 40 watt, fluorescent lamps mounted81/4 inches above the samples. The samples are turned over every morningand evening. The average TLOP of three samples is taken succcessivelylonger time intervals. The samples are placed one foot in front or thesoptmeter and activated by injecting 1.5 part of activator into the bag.Table X sets forth the results.

                  TABLE X                                                         ______________________________________                                        EXPOSURE TIME (HR)                                                                              TLOP (FT-L-HR)                                              ______________________________________                                        YELLOW                                                                         0                68.0                                                         6                47.6                                                        22                40.3                                                        47                33.4                                                        77                27.9                                                        144               25.4                                                        GREEN                                                                          0                44.7                                                         6                39.8                                                        24                36.7                                                        48                32.9                                                        72                30.1                                                        168               26.4                                                        BLUE                                                                           0                 8.19                                                        6                 8.42                                                       24                 7.34                                                       48                 7.29                                                       ______________________________________                                    

EXAMPLE 12 (COMPARATIVE) ABSORBANCE OF MONOPARTICLE STRUCTURES

This example illustrates the different absorptivities of structuresprepared from PVC powder with different particle sizes and differentmolecular weights. The structures are prepared by slurrying together 10parts of a dibutylphthalate solution or oxalate ester and fluorescer asin Example 3 with 10 parts or the PVC powder to be tested The resultingslurries are placed in molds and baked in an oven at 120° C. for 10 min.Square pieces are cut from the cooled structures. The weight of thepieces is recorded. The pieces are soaked in activator solution as infrom Example 1 until their weight pin is constant. The particle size,average molecular weight, parts of activator absorbed per part ofstructure and the physical appearance of the structure are shown inTable XI.

                  TABLE XI                                                        ______________________________________                                                 AVER-      PARTS OF     APPEAR-                                      PAR-     AGE MO-    ACTIVATOR    ANCE                                         TICLE    LECULAR    PER PART OF  OF STRUC-                                    SIZE     WEIGHT     STRUCTURE    TURES                                        ______________________________________                                        0.2-1.5  303,000    0.05         tough, highly                                microns (A)                      plasticized                                  70-75     98,000    0.28         smooth surface,                              microns (B)                      fragile                                      120      104,000    0.45         rough surface,                               microns (C)                      fragile                                      150      205,000    0.62         bumpy surface,                               microns (D)                      very fragile                                 ______________________________________                                    

Larger particle size lives structures that are more porous andabsorptive. The highly absorptive structures are crumbly and friable.The less absorptive structures are very tough and flexible. Thus, it isclear that structures of the desired properties do not result when usingonly single PVC particles regardless of their size or molecular weightas shown in U.S. Pat. No. 3,816,325.

EXAMPLE 13

The following example illustrates the use or combinations of differentPVC powders to prepare chemiluminescent structures. In some of theseformulations, a portion of the PVC powder is dissolved in thechemiluminescent solution prior to adding the resl of the PVC powder andcuring. Four different PVC powders Are used as referred to as A, B, C,and D in Example 12.

Five different formulations are prepared. All or these formulations usethe chemiluminescent solution of Example 3. Formulation No. 1 isprepared by dissolving 1.6 parts or PVC powder A in 87.5 parts or thechemiluminescent solution at 100° C. for 15 min. To this cooled solutionare added 60.9 parts or PVC powder B. Formulation No. 2 is a slurry of46.9 or PVC powder B and 15.6 parts or PVC powder D in 87.5 parts or thechemiluminescent solution. Formulation No. 3 is prepared by dissolving1.6 parts of PVC powder A in 87.5 parts of the chemiluminescent solutionat 100° C., for 15 min. To this cooled solution are added 46.9 parts ofPVC powder der B and 14 parts of PVC powder C. Formulation No. 4 isprepared by dissolving 20.3 parts of PVC powder A in 1096 parts or thechemiluminescent solution at 100° C. for 15 min. To this cooled solutionare added 586 parts of PVC powder B and 175 parts or PVC powder D.Formulation No. 5 is prepared by dissolving 1.6 parts or PVC powder A in87.5 parts of the chemiluminescent Recent solution at 100° C. for 5 min.To this cooled solution are added 60.9 parts of PVC powder D, Astructure is made from each of these formulations by pouring 84.5 partsof slurry into a square mold and curing in an oven at 120° C. for 10min. The absorbency of each of the resultant structures is measured bysoaking a one inch square piece in activator solution until it no longergains weight. The ratio of the weight gain to the initial weight of thetest piece is shown in Table XII, below, along with a description of thephysical appearance of the structure.

                  TABLE XII                                                       ______________________________________                                                    PARTS OF                                                                      ACTIVATOR                                                         FORMULATION PER PART OF   APPEARANCE                                          NO.         STRUCTURE     OF SHEET                                            ______________________________________                                        1           0.22          smooth surface, good                                                          strength                                            .sup.  2C   0.25          slurry settles quickly,                                                       slightly flaky surface                              3           0.33          smooth surface, good                                                          strength, can be folded                                                       without breaking,                                                             slightly stretchy                                   4           0.35          appearance similar to                                                         sheet from formulation                                                        No. 3                                               .sup.  5C   0.68          poor strength, very                                                           flaky surface                                       ______________________________________                                         C = Comparative                                                          

EXAMPLE 14 (COMPARATIVE)

The following example further illustrates the utility in using a varietyof different PVC resins as the dissolved PVC in the formulation. Threedifferent formulations are prepared. All of these formulations use thedubutylphthalate chemiluminescent solution plasticizer of Example 3.Formulation No. 6 is prepared by dispersing 1.6 parts of PVC powder D in87.5 pans of the chemiluminescent solution. The dispersed PVC powder isdissolved in the chemiluminescent solution by heating to 100° C. for 15min. After cooling the solution, there are added 46.9 parts of PVCpowder B and 14 parts of PVC powder D. Formulation No. 7 is prepared bydissolving 1.6 parts of PVC powder C in 87.5 parts of thechemiluminescent solution, as described above. A slurry of this solutionis made by adding 46.9 parts of PVC powder B and 14 parts of PVC powderD. Formulation No. 8 is prepared as described above by dissolving 1.6parts of PVC powder B in 87.5 parts of the chemiluminescent solution.Again a slurry is made from this solution by adding 46.9 parts of PVCpowder B and 14 parts of 35 PVC powder D. A sheet of chemiluminescentmaterial is made from each of these formulations by pouring 84.5 partsof the slurry into a square tray and curing in an oven at 120° C. for 10min. The absorbency of each of these sheets is measured by soaking a oneinch square piece of the sheet in the activator solution until it nolonger gains weight. The ratio of the weight gain to the initial weightof the test piece is shown Table XIII, below, plus description of thephysical appearance of the structure.

                  TABLE XIII                                                      ______________________________________                                                    PARTS OF                                                                      ACTIVATOR                                                         FORMULATION PER PART OF  APPEARANCE                                           NO.         STRUCTURE    OF STRUCTURE                                         ______________________________________                                        6C          0.33         textured (orange peel)                                                        surface, strong, stretchy,                                                    can be folded double,                                                         flaky when cut                                       7C          0.37         smooth surface, breaks                                                        when folded double,                                                           strong, stretchy, flaky                                                       around edges                                         8C          0.33         same as formulation                                                           No. 7                                                ______________________________________                                         C = Comparative                                                          

Strips (1×3 inch) are cut from the above samples. These strips aresealed in polypropylne bags. The chemiluminescent reaction is started byinjecting 1.6 parts of activator solution into the polypropylene bag.The light intensity from these strips is measured with a photometerfocused at the center of the strip. The light intensity is integratedover time to give the total light output (TLOP) in units of foot lamberthours. These light outputs are given for each formulation below.

    ______________________________________                                        FORMULATION NO.  TLOP (FT-L-HR)                                               ______________________________________                                        6                31.6663                                                      7                30.3903                                                      8                36.4072                                                      ______________________________________                                    

EXAMPLE 15

The following example illustrates the results of using mixtures ofdifferent types of PVC powders in preparing sheets of chemiluminescentmaterials. In this example, the PVC powders are simply stirred into aslurry with the chemiluminescent solution. None of the PVC powder isdeliberately dissolved into the chemiluminescent solution prior tomaking the slurry. A variety of different PVC powder mixtures are madefrom PVC powders A, B, and D of Example 10. These different PVC powdersmixtures are slurried with varying amounts of a chemiluminescentsolution and baked in an oven at 120° C. for 10 min. The followingresults are observed.

1) PVC powder A behaves as a binder for the structure. Less than 0.5weight percent of PVC powder A gives flaky, crumbly structures. Over 15weight percent of PVC powder A gives very tough structures which are notabsorbant. The preferred range is about 0.5 to about 3.0, weightpercent.

2) PVC powder B acts as a filler material. It is a moderate binder whennot initially dissolved into the chemiluminescent solution, and it is amoderate absorber.

3) PVC powder D is a very good absorbent, but a very poor binder whennot initially dissolved into the chemiluminescent solution.

EXAMPLE 16 CURING TIME AND TEMPERATURE

This example illustrates the effects of different curing times andtemperatures on the absorptivity and TLOP of the chemiluminescentstructure. All are prepared from Formulation No. 4 of Example 13. TableXIV, below, show the curing times, curing temperatures, and physicalappearance of the sheet.

                  TABLE XIV                                                       ______________________________________                                        TEMP    TIME      APPEARANCE OF SHEET                                         ______________________________________                                         90° C.                                                                        10 min    smooth surface, reasonable strength                          90° C.                                                                        15 min    smooth surface, good strength                               120° C.                                                                        30 min    smooth surface, strong                                      150° C.                                                                         5 min    very strong, tough, flexible, slightly                                        over plasticized                                            150° C.                                                                        10 min    slightly translucent, very strong                                             tough, over plasticized*                                    150° C.                                                                        20 min    translucent, very strong and strong                                           and tough, highly plasticized*                              ______________________________________                                         * = Comparative                                                          

The absorptivities and light outputs are measured for each of thesestructures by the methods described above. The results of each of thesemeasurements are shown in Table XV, below.

                  TABLE XV                                                        ______________________________________                                                             PARTS OF                                                                      ACTIVATOR                                                                     PER PART OF  TLOP                                        TEMP (°C.)                                                                       TIME (MIN) STRUCTURES   (FT-L-HR)                                   ______________________________________                                         90       10         0.27         36.3930                                      90       15         0.30         34.5938                                      90       30         0.32         34.8413                                     120       10         0.35         37.8190                                     150        5         0.17         22.8411                                     150       10         0.02          6.4400                                     150       20         0.02          1.6309                                     ______________________________________                                    

EXAMPLES 17-26

The procedure of Example 3, unless otherwise specified, is followedexcept that different polymer formulations are used. The polymers arespecified below. In each instance, similar results are observed.

17. Polyvinylidene chloride.

18. Copolymer of vinyl chloride and ethylene (80/20).

19. Copolymer of vinylidene chloride and vinyl fluoride (50/50) (largeparticles only).

20. Polyvinyl fluoride (fine particles only). (Example 2 procedurefollowed)

21. Copolymer of vinylidene chloride and propylene (90/10). (Example 4procedure followed).

22. Copolymer of vinyl chloride and vinyl fluoride (95/5) (mediumparticles only).

23. Copolymer of vinyl chloride and vinylidene chloride (75/25).

24. Mixture of polyvinylchloride and polyvinylidene chloride (50/50).

25. Terpolymer of vinyl chloride, vinyl fluoride and vinylene chloride(85/10/5).

26. Mixture of vinylene chloride and polyethylene (75/25).

EXAMPLES 27-37

Following the procedure of Example 2, a series of chemiluminescentdevices is produced using the structures of the above examples, asindicated, in place of the absorbent material thereof. In each instance,comparable results are achieved.

    ______________________________________                                        Example                                                                              Structure of Ex. No.                                                                          Comments                                               ______________________________________                                        27      3 (Blue Fluorescer)                                                                          Even, bright blue light                                28      4 (Green Fluorescer)                                                                         Strong green lumination                                29      6              Yellow light; brilliant color;                                                constant                                               30      9 (Formulation No. 1)                                                                        Strong, yellow light                                   31     10              Constant, even glow                                    32     13 (Formulation No. 4)                                                                        Deep blue light                                                 (Blue Fluorescer)                                                    33     18 (Green Fluorescer)                                                                         Strong light                                           34     19 (Green Fluorescer)                                                                         Strong light                                           35     22 (Green Fluorescer)                                                                         Even, medium light                                     36     25 (Green Fluorescer)                                                                         Bright, green                                          37     26 (Green Fluorescer)                                                                         Good, constant light                                   ______________________________________                                    

We claim:
 1. A flexible, thin, rectangular chemiluminescent devicecomprised of a back sheet of a laminated metal foil having heat sealedthereto, all its edges a bi-component front sheet, the first componentof which is a laminated metal foil capable of preventing the escape ofhydrogen peroxide and the second component of which is a lighttransmitting a polyolefin sheet, said first and second components beingheat sealed to each other at their adjacent latitudinal edge, from about20% to about 50% of the surface area of said front sheet being comprisedof said first component; temporary separation means positioned so as todivide the interior area of said device into two compartments, one undereach of said components, the compartment under said second componenthaving positioned therein an absorbent material containing a solventsolution of a chemiluminescent compound and, optionally, a fluorescer,and the compartment under said first component containing an activatorsolution.
 2. The device according to claim 1 wherein said separationmeans comprises a clamp.
 3. The device according to claim 1 wherein saidabsorbent material is a porous, flexible structure comprising A) anon-particulate phase comprising a polyvinylchloride resin having amolecular weight of about 100,000 to about 500,000 which constitutesabout 0.5 to about .Badd..[.3.0.]..Baddend. .Iadd.15.0 .Iaddend.weightpercent .[.the structure.]. .Iadd.total resin, .Iaddend.B) anagglomerated particle phase comprising either 1) about 85 to about 99.5weight percent .Iadd.of total resin .Iaddend.of polyvinylchloride resinparticles having a diameter of from about 25 to about 125 microns and amolecular weight of from about 50,000 to about 120,000, or mixtures ofsaid particles, or 2) about .Badd..[.40.]..Baddend. .Iadd.45 .Iaddend.toabout 98.5 weight percent .Iadd.of total resin .Iaddend.ofpolyvinylchloride resin particles having a diameter of from about 25 toabout 125 microns and a molecular weight of from about 50,000 to about120,000, or mixtures of said particles, and about to about 40 weightpercent .Iadd.of total resin .Iaddend.of polyvinylchloride resinparticles having a diameter about 130 to about 225 microns and amolecular weight of from about 100,000 to about 225,000 and C) aplasticizer comprising a solvent solution of a chemiluminescent compoundand, optionally, a fluorescer, dispersed throughout both said phases. 4.A structure according to claim 3 wherein said agglomerated particlephase constitute polyvinylchloride particles having a diameter of fromabout 25 to about 125 microns and a molecular weight of from about50,000 to about 120,000, or mixtures of said particles.
 5. A structureaccording to claim 3 wherein said agglomerated particle phaseconstitutes polyvinylchloride resin particles having a diameter of fromabout 25 to about 125 microns and a molecular weight of from about50,000 to about 20,000, or mixtures of said particles andpolyvinyichloride resin particles having a diameter of from about 130 toabout 225 microns and a molecular weight of from about 100,000 to about225,000.
 6. The device of claim 3 wherein said solvent is selected fromdialkyl esters of phthalic acid; ethylene glycol ethers, citric acidesters and tlkyl benzoates and is present in amounts of from about 0.5part to about 3.0 parts per part of resin.
 7. The device of claim 3wherein said solvent is dibutyl phthtlate.
 8. A device of claim 3wherein the chemiluminescent compound is selected from3-aminophthalhydrazide; 2,4,5-triphenlimidazole;10,10'-dialkyl-9,9'-biacridinium salts;9-chlorocarbonyl-10-methylacridinium chloride-andbis(substituted-phenyl) oxalates.
 9. The device of claim 3 wherein thefluorescer is present and is selected from9,10-bisphenylethynylanthracene; 1-chloro-9,10-bisphenylethynylanthracene and2-chloro-9,10-bis(para-methoxyphenyl)anthracene.
 10. The device of claim1 having a self-adhering surface on the outside of said back sheet. 11.The device of claim 1 wherein the chemiluminescent compound isbis(2,4,5-tichloro-6-carbopentoxyphenyl) oxalate.